Polymers of Intrinsic Microporosity with Dinaphthyl and Thianthrene Segments

Abstract

Polymers of intrinsic microporosity with Dinaphtyl and Tianthrene segments Du, Naiying; Robertson, Gilles P.; Pinnau, Ingo; Guiver, Michael D.Contact us / Contactez nous: nparc.cisti@nrc-cnrc.gc.ca. University, Seoul 133-791, South Korea Received August 24, 2010; Revised Manuscript Received September 11, 2010 ABSTRACT: Novel intrinsically microporous homopolymers and copolymers derived from PIM-1 monomers (5,5 0 ,6,6 0 -tetrahydroxy-3,3,3 0 ,3 0 -tetramethylspirobisindane and 2,3,5,6-tetrafluoroterephthalonitrile) with two additional monomers;tetrahydroxydinaphthyl and tetrafluorotetraoxide thianthrene;are reported as potential materials for membrane-based gas separations. The resulting copolymers prevent efficient space packing of the stiff polymer chains and consequently exhibit analogous behavior to that of PIM-1, the most widely reported polymer in this class of materials. In addition, the copolymerization provides high molecular weight copolymers and low polydispersity if the polymerization reactions were conducted at elevated temperature for an extended period of time. Detailed structural characterization of the new monomers and polymers was determined by 1 Ha n d 19 F nuclear magnetic resonance spectroscopy (NMR). The thermal properties were detected by differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). Polymer free volume was calculated from the polymer density and specific van der Waals volume. Under the same testing conditions, the homopolymer containing thianthrene units and most of the analogous copolymers have an excellent combination of properties with good film-forming characteristics. The gas transport properties show higher selectivity for gas pairs such as O 2 /N 2 ,C O 2 /N 2 , and H 2 /N 2 with a corresponding decrease in permeability compared to PIM-1. This work also demonstrates that significant improvements in properties may be obtained through copolymers of intrinsic microporosity (CoPIM)s. Furthermore, this work extends the spectrum of high molecular weight soluble PIMs beyond those reported previously.

Synthesis, characterization, and gas permeation properties of adamantane‐containing polymers of intrinsic microporosity

“…IR spectra were recorded using Bruker a-T spectrophotometer in the range 4000-600 cm 21 . 1 H and 13 C NMR spectra were recorded using a Bruker-AV 200 MHz or 400 MHz spectrometer in CDCl 3 or dimethyl sulfoxide (DMSO-d 6 ) with tetramethylsilane as an internal standard.…”

“…Molecular weights and dispersity values of PIMs were obtained from gel permeation chromatography (GPC) equipped with spectra series UV 100 and spectra system RI 150 detectors using chloroform as an eluent and polystyrene as the standard. The sample concentration was 2 mg mL 21 . X-ray diffractograms of powder samples were recorded on a Rigaku Dmax 2500 with scan rate of 28 min 21 .…”

“…The sample concentration was 2 mg mL 21 . X-ray diffractograms of powder samples were recorded on a Rigaku Dmax 2500 with scan rate of 28 min 21 . TGA was performed using Perkin-Elmer TGA-7 system at a heating rate of 10 8C min 21 under N 2 atmosphere.…”

“…PIM-1 is a widely studied candidate in the class of PIMs due to its rigid and contorted structure. 9 Since then, several examples of PIMs containing units such as triptycene, 10,11 spirobisindane, 12,13 Tr€ oger's base, [14][15][16][17] spirobischromane, 18 spirobifluorene, 19 hexaphenylbenzene, 20 naphthalene, 21 tetraphenylethylene, 22 phthalimide, 23 tribenzotriquinacene, 24 cardo PIMs, and so on 25 have been synthesized and evaluated as membrane materials for gas separation.…”

Photo-oxidative enhancement of polymeric molecular sieve membranes

“…Currently, there are several strategies to improve the separation performance of PIMs membranes: (i) enhancing the rigidity of polymer chain by synthesis of new monomers 12,[27][28][29][30] , (ii) postsynthetic modification of PIMs polymer 10,25,31 , (iii) mixed matrix membranes [32][33][34] and (iv) crosslinking induced by chemical 35 or heat treatment 36 . Ultraviolet light irradiation is a widely used technique for processing of polymer materials 8,[37][38][39][40] , for example, polymerization of novel gas-separation membranes 40 , creating nanostructures from block copolymer 8 , or surface modification of polymeric films (for example, polyimides and polydimethylsiloxane) 8,[37][38][39] .…”